Color photographic light-sensitive material containing ultraviolet absorbing agents



United States Patent ()1 lice 3,533,794 Patented Oct. 13, 1970 3,533,794 COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MA- TERIAL CONTAINING ULTRAVIOLET ABSORB- ING AGENTS Reiichi Ohi, Hiroyuki Amano, Kazuo Shirasu, and Yasushi Oishi, Kanagawa, Japan, assignors to FUJI Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed Mar. 25, 1969, Ser. No. 810,343 Claims priority, application Japan, Mar. 25, 1968, 43/ 19,299 Int. Cl. G03c 1/84 U.S. CI. 96-84 15 Claims ABSTRACT OF THE DISCLOSURE A color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds represented by the general formula:

R; and R can be hydrogen or up to a four carbon atom alkyl group. R, can be hydrogen or a halogen. An organic solvent having a high boiling point is also present.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a color photographic lightsensitive material containing ultraviolet absorbing agents, and particularly to a color photographic light-sensitive material containing at least two ultraviolet absorbing compounds selected from Z-aryl benzotriazole derivatives.

Description of he prior art The light-fastness property of color photographic images is inferior to that of black and white photographic images made of metallic silver. This is due to the fact that color photographic images are made from coloring materials formed by the coupling reaction between couplers and oxidation products of developing agents, that is, by a color development. It has been suggested, to overcome this defect, to add ultraviolet absorbing agents to the color photographic light-sensitive materials in order to protect the color image from the harmful effects of ultraviolet rays. To accomplish this, there are two general methods, one of which comprises applying to, or impregnating in, color prints or transparent color positives ultraviolet absorbing agents after color processing. The other method comprises incorporating ultraviolet absorbing agents into the photographic light-sensitive materials at the time of manufacture. This invention relates to the latter method.

Ultraviolet absorbing agents incorporated into photographic light-sensitive materials must have the following properties.

(1) They must eifectively absorb ultraviolet rays in the range of 300-400 Il'1,u, must not absorb visible rays of over 420 mg.

(2) They must neither flow out nor change color during processing.

(3) Ultraviolet absorbing agents must not color themselves, and their ultraviolet absorptivity should not lower under exposure to light.

(4) They must not have a harmful influence upon the photographic light-sensitive material during preparation, storage, or processing.

Though many compounds are known as ultraviolet absorbing agents, few compounds satisfy the demands of the aforesaid four items. Many commercial ultraviolet absorbing agents flow out during developing treatment, and some of these compounds have a harmful influence upon the photographic light-sensitive material.

As shown in U.S. Pat. 3,004,896, Z-aryl benzotriazole derivatives are excellent ultraviolet absorbing agents. Further, it is known (see U.S. Pat. 3,253,921) that oilsoluble derivatives of said compounds having a long chain alkyl group can be added to the photographic lightsensitive material in the form of a dispersion.

However, the compounds having a comparatively low molecular weight which are described in U.S. Pat. 3,004,896 do not have sufficient solubilities in the desired organic solvents having a high boiling point (for example, dibutyl phthalate, tricresyl phosphate, etc.). Accordingly, a large amount of the solvent is required in order to dissolve these compounds, therefore, the amount of gelatin needed for dispersion increases, and consequently, the thickness of the layer of the photographic sensitive materials increases. These facts are very undesirable in view of the definition or sharpness of the resultant image and the cost of production.

On the other hand, when organic solvents having a lower boiling point (for example, ethyl acetate) are used as a solvent assistant together with the above organic solvents which have a higher boiling point (to increase the solubility of the ultraviolet absorbing compounds with a comparatively low molecular Weight described in U.S. Pat. 3,004,896), the solvent mixture is dispersed in an equeous gelating solution and the dispersion is coated as a supersaturated solution (the solution including the ultraviolet absorbing agent in an over-saturated state in the organic solvent having a high boiling point), there is apt to occur crystallization, and consequently the capacity of the gelatin layer is harmed by separation of crystals in the gelatin layer.

As methods for overcoming these disadvantages. there have been known methods for preventing crystallization by introducing alkyl groups having a large number of carbon atoms (for example, an isooctyl group, hexadecyl group or two tertiary amyl groups) as the substituent to form the 2-aryl benzotriazole derivatives (see U.S. Pat. 3,253,921). However, the molecular Weight of these compounds increases due to the introduction of the higher alkyl groups which do not contribute to ultraviolet absorbing property thereof. Accordingly, the weight of added compound increases, and consequently, the amount of the solvent and gelatin increases as well as the thick ness of the layer of the photographic material. Therefore, it is not practical to use these compounds in view of the production cost and the lack of definition or sharpness of the image formed in the photographic material.

3 SUMMARY OF THE INVENTION The present invention comprises a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:

N OH R3 l K/ N Br R and R can represent a member selected from the group consisting of a hydrogen atom and an alkyl group having up to four carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom. An organic solvent having a high boiling point is also present.

If the material comprises at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of these should contain a dispersion of the ultraviolet absorbing compounds.

Alternatively, if an outer gelatin layer is utilized, the gelatin layer may contain a dispersion of at least two of the ultraviolet absorbing compounds.

As another alternative, where a gelatin layer is superimposed on a surface of a support for a light-sensitive material, the gelatin layer being on the surface of the support opposite the photographic silver halide emulsion layer, the gelatin layer can contain a dispersion of at least two ultraviolet absorbing compounds.

One object of this invention is to provide a color photographic light-sensitive material containing a dispersion of ultraviolet absorbing agents having a comparatively low molecular weight.

Another object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which absorb ultraviolet rays of 300- 400 m but which do not absorb visible rays of over 420 Ill 1..

A further object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which do not flow out or discolor during processing, which do not color or deteriorate with respect to ultraviolet absorptivity by exposure, and which do not have any harmful influence upon the photographic light-sensitive material during preparation, storage or processing.

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to this invention, the objects can be accomplished by the use of a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the following formula, and an organic solvent having a high boiling point:

tedly found that if two or more species of 2-aryl benzotriazole derivatives having lower molecular weights, rep- Compound 1 Compound 3 N OH 01 2-(2'#hydroxy-3'-tert-buty1-5'-methyl phenyl)-5- chlorobenzotniazole Compound 4 N OH 01 The compounds of this invention can be produced by the general method disclosed in US. Pat. 3,004,896.

The organic solvent having a high boiling point used in this invention are such as those described in 11.8. Pat. 2,322,027. The preferred solvents include di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-ocresyl phosphate, diphenyl mono-p-tert-butyl phenyl phosphate, monophenyl di-p-tert butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tert-butylphenyl phosphate, tri-o-phenylphenyl phosphate, di-p-tert-butylphenyl mono (5-tert-butyI-Z-phenylphenyl)phosphate, etc.

The low boiling organic solvents, such as methanol, ethanol, ethyl acetate, butyl acetate, diethylether, dioxane, tetrahydrofuran, acetone, methylethyl ketone, ethylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether may be used as the solvent assistant.

In the following, the solubilities of these compounds alone in dibutyl phthalate and the solubilities of mixtures of two or more of said compounds in dibutyl phthalate are compared.

and 4 0.75

It is obvious from the results of this experiment that solubility increases by mixing two or more compounds.

From the results of the above experiment, Compound 1 exhibits a comparatively high solubility for dibutyl phthalate. However, as described in US. Pat. 3,253,921, a stable dispersion thereof cannot be produced even if a solution thereof in an organic solvent having a high boiling point is produced by dissolution at a high temperature because of the rapid separation of the crystals from the super-saturated solution. In order to examine the stability of the supersaturated solution, the following examination took place.

Experiment 2 1.0 ml. of dibutyl phthalate and the test compounds were enclosed in a glass tube having a 0.5 cm. inner diameter, and heated to 100 C. to completely dissolve.

The material was then rapidly cooled by immersion in ice-water, and was then allowed to stand at 5 C. in a refrigerator. The separation of crystals was thus observed.

(1) Use of 1.0 g. of Compound 1. Crystals began to separate immediately after cooling, and the contents solidified completely after minutes.

(2) Use of 0.5 g. of Compound 1. Crystals began to separate at 10 minutes after cooling, and the contents solidified completely after one hour.

(3) Use of a total of 1.0 g. consisting of 0.5 g. of Compound 1, 0.25 g. of Compound 2, 0.15 g. of Compound 3 and 0.1 g. of Compound 4. Crystals began to separate 3 hours after cooling, but the contents did not solidify within one month.

(4) Use of a total of 0.5 g. consisting of 0.25 g. of Compound 1, 0.125 g. of Compound 2, 0.075 g. of Compound 3 and 0.05 g. of Compound 4. Crystals did not begin to separate within one month.

It is clear by this experiment that the stability of the supersaturated solution is superior when two or more of 2-aryl benzotniazole derivative represented by Formula 1 are used. In order to confirm this fact in practical use, the following experiment was carried out.

Experiment 3 10 g. of Compound 1 was dissolved in 10 cc. of dibutyl phthalate and cc. of ethyl acetate by warming. The solution was added to a mixture of 200 cc. of a 10% aqueous solution of gelatin and 20 cc. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed with a colloid mill and applied to a triacetyl cellulose film, dried, and was called Sample A. By the same procedure as in preparing Sample A, Sample B was pre pared using 4 g. of Compound 1, 2 g. of Compound 2, 2 g. of Compound 3 and 2 g. of Compound 4: Total 10 g. instead of the 10 g. of the Compound 1.

As a result of comparing Sample A with Sample B, in Sample A Compound 1 crystallized during drying and a coated layer became opaque, while in Sample B the dispersion was stable, consequently opaqueness due to separting crystals was not observed after being allowed to stand for a long period of time (over 3 months).

It is clear from the above experiments that 2-aryl benzotriazole derivatives represented by Formula 1 used as ultraviolet absorbing agents for color photographic lightsensitive material do not crystallize if two or more of said compounds are used together. It is not as effective to use two or more of the Z-aryl bezotriazole derivatives when the mixing ratio of a compound which is the minimum component is less than 5%, or the mixing ratio of the compound which is the maximum component is over Accordingly, when two or more 2-aryl benzotriazole derivatives are used as ultraviolet absorbing agents for photographic light-sensitive materials, the mixing ratio of these compounds is preferably in the range of from 5% to 90%.

The 2-aryl benzotriazole derivatives may be used in the range of 1-100 mg./ cm. preferably 5-50 mg./ 100 cm. in forming the film.

The preferred embodiments and the advantages of this invention will now be described in the following examples.

EXAMPLE 1 To a baryta-coated paper, a blue-sensitive silver bromide gelatin emulsion layer containing a yellow coupler: 5-(p-octadecycloyl-aminobenzoyl acetamino) isophthalic acid, a gelatin intermediate layer, a green-sensitive silver bromoiodide gelatin emulsion layer containing a magenta coupler: 1-(3-sulfo-4-phenoxyphenyl)-3-heptadecyI-S-pyrazolone, a gelatin intermediate layer, and a redsensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler: N-octadecyl-1-hydroxy-4- sulfo-Z-naphtamide were applied, in the order recited. The obtained coating was divided into two samples, to one of which there was applied a dispersion containing ultraviolet absorbing agents produced by the following procedure so as to contain 20 rug/100 cm. of the ultraviolet absorbing agent. To the other there was applied only a gelatin solution for use as a protective layer.

The dispersion containing ultraviolet absorbing agents was prepared as follows: 30 g. of Compound 1 and 15 g. each of Compounds 2 and 3 were dissolved in a mixture of 80 g. of dibutyl phthalate and 200 g. of butyl acetate by heating. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed using a colloid mill to produce a homogeneous dispersion.

Sample coatings thus obtained were given exposure to light through blue, green and red step wedges. The samples were then developed with a color developer containing N,N diethyl p phenylene-diamine, and then washed with water, fixed, washed with water, bleached, washed with water, hardened, washed with water and dried by state of the art methods. After the samples were exposed directly to sunlight for 30 hours, the reflection density thereof was measured at three points (0.5, 1.0 and 1.5 reflection density) for each sample before re-exposing to light. A decreasing density ratio was calculated by dividing the balance of the density before exposure and the density after exposure by the density before exposure.

The calculated decrease of density ratio is shown in the following table.

Density before exposure 0. 5 1. 0 1. 5 Sample containing ultraviolet absorbing agents,

percent:

percent:

Cyan 18 15 15 Magenta. 8 8 8 Yellow. 40 40 36 the sample including the ultraviolet absorbing agents, coloring was not observed (blue density 0.04). If the ultraviolet absorbing agents were not incorporated into the protective layer but into the intermediate layer between the light-sensitive emulsion layers, fading of the image dyes in the under layer of this intermediate layer was prevented.

EXAMPLE 2 Into the color printing paper described in Example 1, a dispersion containing ultraviolet absorbing agents prepared by the following procedure was added (in the amount of 10 mg./100 cm. of the ultraviolet absorbing agents to the uppermost light-sensitive emulsion layer containing a cyan coupler). The uppermost protective layer was formed of gelatin alone. The same examination was carried out as in Example 1.

The dispersion described above was prepared" as follows: 30 g. of Compound 1, 10 g. of Compound 2, 10 g. of Compound 3 and 10 g. of Compound 4 were dis-solved (by heating) in a mixture of 60 g. of dibutyl phthalate and 100 g. of ethyl acetate. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed with a colloid mill to obtain a homogeneous dispersion.

The decrease in the ratio of color density, calculated by the same method as in Example 1, is shown in the following table.

Further, the photographic properties of the red-sensitive emulsion layer were not influenced by the addition of Compounds 1, 2, 3 and 4.

EXAMPLE 3 To one surface of a triacetyl cellulose film, a redsensitive silver chlorobromide emulsion layer containing a cyan coupler: l-hydroxy-2-(3'-2", 4"-5-amylphenoxy propyl) naphtamide, a gelatin intermediate layer, a greensensitive silver chlorobromide emulsion layer containing a magenta coupler: 1-phenyl-3-(3-(N-butylcapryl-amide propionamide) )-5-pyrazolone, a gelatin intermediate layer a blue-sensitive silver iodobromide emulsion layer containing a yellow coupler: benzoylaceto-2-chloro-5-dodecyloxycarbonyl anilide and a gelatin protective layer were applied, in the order recited. The couplers were used as a solution of dibutyl phthalate. To the other surface of the film, a dispersion containing the ultraviolet absorbing agents used in Example 1 was applied in an amount of 30 mg./100 cm. of the ultraviolet absorbing agent. The film was then dried.

The color film thus obtained was exposed to light through blue, green and red step wedges. The exposed film was then developed with a developer containing 4- amino-3-methyl-N,N-diethylaniline, washed with Water, fixed, washed with water, bleached, washed with water, and dried by conventional state of the art methods. The sample thus obtained was exposed for 50 hours to a xenon are by facing the second surface of the sample to the source of light. A decrease in the ratio of the color density of this sample was compared with that of the sample which did not have the ultraviolet absorbing layer on the second surface. The decrease in the ratio of the color density, which was calculated by the same method as in Example 1, is shown in the following table.

It is clear from the above examples that the fastness to light of the color images had been remarkably improved by using the ultraviolet absorbing agents according to this invention.

To further illustrate some of the preferred forms of the present invention, the boiling point for the solvent in the most preferred form of the invention should be a minimum of C., under normal atmospheric pressure.

Further, in the most preferred form of the invention the solvent is generally present in an amount less than three times the amount of coupler. However, it is specifically stated at this point that the amount of solvent can vary from this range, and that amounts greater than three times the amount of coupler are operable.

With respect to the amount of the solvent assistant utilized, this is determined purely on a practical basis, i.e., when necessary an amount suflicient to dissolve the coupler is utilized. This range cannot be defined with greater specificity.

What is claimed is:

1. A color photographic light-Sensitive material which comprises a support, at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of either the emulsion layers or the colloid layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:

wherein R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.

2. A color photographic light-sensitive material which comprises an opaque film support, at least one photographic silver halide emulsion layer superposed on said support, and an outer gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:

N O H wherein R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.

3. A color photographic light-sensitive material which comprises a transparent film support, at least one photographic silver halide emulsion layer superposed on said support, and a gelatin layer superposed on the other surface of said support, said gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:

wherein R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.

4. A color photographic light-sensitive material as claimed in claim 1, wherein said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroXy-5-tert-butyl phenyl)benzotri azole, 2-(2'-hydroxy-3,5'-di-tert butyl phenyl)benzotriazole, 2-(2'-hydroXy-3-tert-butyl-5'-methyl phenyl)-5- chlorobenzotriazole and 2-(2-hydroXy-3,5-di-tert-butyl phenyl -5-chlorobenzotriazole.

5. A color photographic light-sensitive material as claimed in claim 4 wherein said layer contains from about 1l00 mg./ 100 cm. of said ultraviolet absorbing compounds.

6. A color photographic light-sensitive material as claimed in claim 1 wherein said layer contains from about ll rug/100 cm. of said ultraviolet absorbing compounds.

7. A color photographic light-sensitive material as claimed in claim 1, wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenylphenyl phosphate and di-p-tert-butylphenyl mono(5-tert-butyl-2-phenylphenyl) phosphate.

8. A color photographic light-sensitive material as claimed in claim 2 wherein said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroxy,5-tert-butyl phenyl)benzotriazole, 2 (2'- hydroxy-B,5-di-tert-butyl phenyl)benzotriazole, 2 (2- hydroXy-3-tert-butyl-5'-methyl phenyl) 5 chlorobenzotriazole and 2-(2-hydroxy3',5-di-tert-butyl phenyl)-5- chlorobenzotriazole.

9. A color photographic light-sensitive material as claimed in claim 2 wherein said layer contains from about 10 1-100 mg./ cm. of said ultraviolet absorbing compounds.

10. A color photographic light-sensitive material as claimed in claim 2 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butylphenyl mono(S-tert-butyI-Z-phenyI-phenyl) phosphate.

11. A color photographic light-sensitivematerial as claimed in claim 3 wherein said ultraviolet absorbing compounds are members selected from the group consisting of 2- (2-hydroxy-5 -tert-buty1 phenyl benzotriazole, 2- (2'- hydroxy-3',5-di-tert-butyl phenyl) benzotriazole, 2-(2'- hydroxy-3'-tert butyl-5-methyl phenyD-S-chlorobenzotriazole and 2-(2'-hydroxy-3,5-di-tert-butyl phenyl)-5- chlorobenzotriazole.

12. A color photographic light-sensitive material as claimed in claim 3 wherein said layer contains from about 1-100 mg./ 100 cm. of said ultraviolet absorbing compounds.

13. A color photographic light-sensitive material as claimed in claim 3 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-ptert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butyl-phenyl mono(S tert-butyI-Z-phenyl-phenyl)-phosphate.

14. The color photographic light-sensitive material of claim 1 wherein said solvent has a boiling point of at least C. under normal atmospheric presure.

15. The color photographic light-sensitive material of claim 1 wherein the mixing ratio of said ultraviolet absorbing compounds is in the range of from 5% to 90%.

References Cited UNITED STATES PATENTS 3,004,896 10/1961 Heller et al. 252300 XR 3,244,524 4/1966 Trucker et al 9684 3,253,921 5/1966 Sawdey 252-3()0 XR RONALD H. SMITH, Primary Examiner U.S. Cl. X.R. 25230O 

